Process of producing surface coverings containing oxygen-convertible synthetic resins



Patented July 25, 1944 rnocnss 0F, rnonucmo 'suarscmoovenmos CONTAININGoxrasmcommu- BLE SYNTHETIC SIRS Theodore F. new, Stamford, Coma,aill'nor to" American Company, New York,

' N..Y.,'aoorporation orllaine v ho Amvlica'tlonlayuJm,

SeriaiNm 888.24: p

invention relates toan improvement in "jhfl'htiillttiilfe of surfacecovering compositions on its return to such as. floor coveringcompositions conmmns t fsieca'tive binders'which comprise a Synthetic.

Previous attempts to 'producefloor coverings theiike synthetic have notentirely successluh, It has not enerally feasible to obtain materialswhich have the proper decree-oi flexibility; and yet which are j I v,number or 8"01." leslis reached. is

suiliciently cured or fseas'oned'j," suitable tor the ordinary usesolsuch materials.

isj'very dimcult to obtamssummr sheeting andthe products which areobtainedare still and brittle after beina maimed." 7 An object of myinvention is to produce surresistan'ce as be satistactory tor the usesvoi such materials.

Another object of; invention is. to provide compositions whichm'aybecall! toll" homoa eneous sheets which may bsubjjected to the ordinaryhandling without erumblinl' or breakina.

These and other object-care attainedby oxidisin: and/or polymerizing asiccativebinder comprising an Orw ll-convertible synthetic resin, mixingthe resulting materiat with tillers sheetin: the mixture and seasoninai'the sheeted mixture. The distinguishing ieature 'oimy invention is theoxidation and/or polymerisation;

stepvwhich'precedesthe admis'ture oi tillers and other steps oi theprocess. I

The following example in whichfthe proportlons are in parts by weight isaivenrby way oi,

The terpene, fu'maric acid and glycol are heated 7 under reflux andpreferably in an inert'atmos phere in the presence of the p-toluenesulfonic acid as a catalyst. The apparatus in which the reaction iscarriedout preferably hasa water p or to'my invention'ithas beeneustomjsryto' I mixan oxya'eneconvertible synthetic resin men '1' -Blewvdrrw with iillers, sheeting and then-seasonin" the sheetcd material.Using this process, it

tion is continuously separated and removed iron the reactants and thereaction products; The condensation and esteriflcatibh are continueduntil the acid number is less than about 10. The

unreacted Pinene is as and the linseed oil latty'aclds. toaether' withthe glycerol, are 7 added to the resin. The reaction mixture is thenninintaind at about 200-'-25' Ci acid Cl, prclelably in a "Wood andBedflird kettle."

mice

p the reaction chamben By the-water romeo during th'eco'ndensa- Anysimilar type of apparatus may be 53 ,110!

example; one havina the iollowine description:

cylindrical vesselis mounted with its axis l horizontal and is providedwith an umor which a so i'ace coverings which have suiilcientflexibility,

anj'axle'placed along the'axis off-the cylindrical'container and havinablades or spokes attached theretog'ea'chol which is at a; "convenientanzle, e. a. 45 C. to each of the adjacent blades; The anleisdriven byany convenient means. but prelerably by means 0! an=electric motorprovided with areductionaear'hiechanism. The cylindrical container isprovided with 'anair" inlet, preierably at one end of 'thetop oi. thecontainer and an air outlet at the other code! the container; {Thevcylindrical container is preferably enclosed in arjacket through whicha heat exchange medium may be circulated. Thisheat exchanaemedium may beeither a heating medium to raise the temperature at the beginning or theoxidation and/or polymerisation or it may be a cooling medium in orderto lower the temperature toward the cadet the reaction when thetemperature is from the bottom part.

trap through which the reflux condensate passes l6 Initially theagitator speed is preferably about 30012 P. ll. The speed' ot theagitatoris'gem erally maintained at this point untll the resin beings tobecome viscous. The speed'is then gradually reduced as the resinoxidizes and/or polymerizes until a speed oi about 100 R. P. M. isreached. The reduction in'speed may be conveniently regulated uselectric motor he to drive-the agitator 'bykeeplng the power con-(square inches) e the resinhave a viscosity of,0.5 (square inches)according to the test Just described. Composi- Prior to introducing theresin into the Wood and Bedford kettle, it is usually desirable to add asmall proportion of a suitable drier such as cobalt naphthenate, leadnaphthenate or mixtures of-these or other oil solubledriers. The resinmaybe exposed to ultra-violet light during the oxidation and/ orpolymerization. The oxidation and/or polymerization is continued until Ythe resin attains a viscosity which is suitable for use in theproduction of surface coverings;

The viscosity may be: conveniently measured by placing a quarter of agram sample between two flat glass plates about-4 inches. square and um.See the Federal Stock Catalogue, section 4, Part 5 DD. LLL-Ir351 et seq.and pp. ILL-L361 et seq. for the method employed herein. The timerequired for "seasoning a 2 mm. sheet of the composition described.above is about twenty to thirty days. The resulting seasoned" surfacecovering has an alkali resistance of about .28 mm.

; penetration. The alkali resistance may be determined by measuring thedepth in mm. to which subjecting to pressure between platens maintainedat a temperature of 210-215 Crfor five minutes under a load of about 4.5kilograms.

The area over which the resin spreadsis meas ured by a planlmeter andthis value is squared. The results are, therefore, expressed in units ofGenerally itis preferable that tions which are suitable for theproduction of satisfactorysurface coverings should have a viscosity of0,24 square inches)! determined by the method outlined. At thisstageitis suitable 'zoctadecandiol, etc. and suitably modified withoilfatty acids or, in some instances, with foruse-as a binder forsurfacecoverings. .It is I sometimes advantageous to allo w.,thepolymeriz ed binder to age for from about three days to about threeweeks'betore use. The apparatus for ,measuringtheviscosity. of the resinis de- -scribed in detaildn the application of Robert BowlingBarnesSerial ma -41a filed May 28, I938. I.

, The aforementioned ,application of Bobert Bowling Barnes. describes amethod whereby after several viscosity measurements have been above, thevalues obtained .(i. e. the squared val ues) areplotted as the mantissaand the time of processing as the abscissa. A smooth curve is obtainedand, therefore, theftime necessary to V completethe oxidation and/orpolymerization to any desired point maybe obtained by extrapolation. 7The incorporation of this procedure in my Iprocess of producing surfacecovering composi tions is obviouslyadvantageous; and it enables onetoobtain accurate control of the processing of v} e'compositions: j

Preparation of sheetedsur/ace covering Y Parts Binder v Wood flour 30Lithopone Whiting 20 These substances with or without a small proportionof drier, e. g. 0.1% of cobalt naphthenate,

' are mixed together, e. g. in an internal mixer.

The compacted mass thus obtained may be disinthe drying oils themselves.Such resins may, of course,-be modified-in any of the knownways withmonobasic acids and monohydric alcohols as desired. Generally I havefound that resins made by the reaction of fumaric acid, triethylene dglycol and a non-conjugated terpene hydrocarbon of the CmHis series, e.g. a and sp'inene, dipentene, limonene, and terpinene, are'particularlysuitable. Oi these, superior resins are usually obtained with dipentene,and p'-' pinene.

Obviously, mixtures of these may be employed,

' particularly such mixtures as maybe obtained in "the variouscommercial grades of terpenes which m'ade at short intervalsof time withthe api paratus described thereinand briefly set forth tegrated as by aset or "scratch rolls" which comprises. a plurality of v rolls. havingintermeshing teeth projecting fromtheir surfaces. The resulting materialis sheeted on calender rolls or optionally it may be furtherdisintegrated and then calender-ed. The material may be calenample.

are obtained by fractional distillation." Itis also possible to use theconiugate'dhydrocarbons of the CioHu' seriespe. g. 'aandfiephellandrene,

a-terpinene, n fi p-menthadiene. etc. Furthermore, maleic acid ormaleic' anhydride may be used in place of the fumari'c acid, althoughsuperior results are obtained'it fumaric acid be used. Among the dryingoils or the acids derived therefrom which may besubstituted for part orall of those used in. the above example are included the following:menhaden, sardine or similar fish oils, tung oil, soyabean oil, perillaoil, oiticica oil, dehydrated castor oil, sunflower-seed oil, etc.Obvoiusly variousmixtures of the drying oils or mixtures of the dryingoil acids may be substituted" for the single drying oils ordrylng oilacids. Drying oil acids which have a relatively highiodine number andwhich are liquid at about 5 C. may be substituted for all or part of thedrying oil fatty acids used in the above ex- The term drying oil" asused herein is intended to include not only all drying oils, but alsothe semi-drying oils. In some instances-it may be desirable to usemixtures of a drying oil and a fatty oil of the non-drying type.

- Natural resins or gums, e. g. rosin, Kauri gum,

- Congo gum, ester gum, abietic acid its esters, pi-

dered'onto'burlap or other fibrous backing if deand The sheeted materialis placed in a stoving oven throushwhic'li aiourrent of 'hea'tedflair at7 about C.-90 C. is circulated until thematerial is completelyseasoned," i. e. until the sheet acquires the necessarydegree'ofhardness.

The hardness may be measured by any ofv the methods employed in themanufacture of linole- =maric acid, etc., may be admixed I thetlc resinbinders. V

Other fillers may be substituted for part or all with the synof thatused in the above example, e. g. cork, alpha cellulose pulp, asbestos,cottonwood tree pulp, walnut shell meal, glass fibers, foliated glass,etc. Various pigments may be substituted "for part or all of that usedin the above example, e. g; lithopone, barytes, zineoxide, titaniumoxide, chromates, red lead, white lead, malachite green, chrome yellow,chrome green, Prussian composition which comprises heating with meblue,iron oxide, as well as various dyes. lakes. etc.

The term "seasoning" as applied to surface covering compositionsindicates the process 0! curing by heatina to polrmerise and/or oxidisethe composition to a stage wherein the surface covering is sufi'icientlyhard and resistant to abrasion to be suitable for its intended purposeand yet is still sufiiciently flexible to permit the usual bending androllinl required of surface covering material.

Obviously many modifications and variations chanical asitation in thepresence of oaysen a in the processes and compositions described abovemay be made without departing from the spirit and scope oi the inventionas defined in the appended claims.

I claim:

1. A process of producing a surface coverlna

